High-pressure Small-angle Neutron Research Articles

A high-temperature high-pressure small-angle neutron scattering cell for studying hydrothermal reactions in supercritical water

A high-temperature high-pressure cell equipped with a metallic window was developed for small-angle neutron scattering (SANS). The feasibility of a Ti alloy (Ti–6Al–4V) as a candidate window material was assessed, considering its mechanical strength and neutron characteristics. SANS experiments should be conducted using safe and reliable materials without risk of window damage or leakage of the activated samples due to window breakage. SANS profiles measured for supercritical heavy water showed maximum scattering intensity at temperatures and pressures near the critical density. Additionally, the utility of the cell for observations of the decomposition of plastic in supercritical water is presented. The cell facilitates analysis of reaction mechanisms under sub- and supercritical conditions, which could provide detailed information to aid efficient decomposition and recycling, contributing to a sustainable society.

Structure of proteins under pressure: Covalent binding effects of biliverdin on β-lactoglobulin

High pressure (HP) is a particularly powerful tool to study protein folding/unfolding, revealing subtle structural rearrangements. Bovine β-lactoglobulin (BLG), a protein of interest in food science, exhibits a strong propensity to bind various bioactive molecules. We probed the effects of the binding of biliverdin (BV), a tetrapyrrole linear chromophore, on the stability of BLG under pressure, by combining in situ HP small-angle neutron scattering (SANS) and HP-UV absorption spectroscopy. Although BV induces a slight destabilization of BLG during HP-induced unfolding, a ligand excess strongly prevents BLG oligomerization. Moreover, at SANS resolution, an excess of BV induces the complete recovery of the protein “native” 3D structure after HP removal, despite the presence of the BV covalently bound adduct. Mass spectrometry highlights the crucial role of cysteine residues in the competitive and protective effects of BV during pressure denaturation of BLG through SH/S-S exchange.

Design of Surfactant Tails for Effective Surface Tension Reduction and Micellization in Water and/or Supercritical CO2.

The interfacial properties and water-in-CO2 (W/CO2) microemulsion (μE) formation with double- and novel triple-tail surfactants bearing trimethylsilyl (TMS) groups in the tails are investigated. Comparisons of these properties are made with those for analogous hydrocarbon (HC) and fluorocarbon (FC) tail surfactants. Surface tension measurements allowed for critical micelle concentrations (CMC) and surface tensions at the CMC (γCMC) to be determined, resulting in the following trend in surface activity FC > TMS > HC. Addition of a third surfactant tail gave rise to increased surface activity, and very low γCMC values were recorded for the double/triple-tail TMS and HC surfactants. Comparing effective tail group densities (ρlayer) of the respective surfactants allowed for an understanding of how γCMC is affected by both the number of surfactant tails and the chemistry of the tails. These results highlight the important role of tail group chemical structure on ρlayer for double-tail surfactants. For triple-tail surfactants, however, the degree to which ρlayer is affected by tail group architecture is harder to discern due to formation of highly dense layers. Stable W/CO2 μEs were formed by both the double- and the triple-tail TMS surfactants. High-pressure small-angle neutron scattering (HP-SANS) has been used to characterize the nanostructures of W/CO2 μEs formed by the double- and triple-tail surfactants, and at constant pressure and temperature, the aqueous cores of the microemulsions were found to swell with increasing water-to-surfactant ratio (W0). A maximum W0 value of 25 was recorded for the triple-tail TMS surfactant, which is very rare for nonfluorinated surfactants. These data therefore highlight important parameters required to design fluorine-free environmentally responsible surfactants for stabilizing W/CO2 μEs.

Reduced methane recovery at high pressure due to methane trapping in shale nanopores

By 2050, shale gas production is expected to exceed three-quarters of total US natural gas production. However, current unconventional hydrocarbon gas recovery rates are only around 20%. Maximizing production of this natural resource thus necessitates improved understanding of the fundamental mechanisms underlying hydrocarbon retention within the nanoporous shale matrix. In this study, we integrated molecular simulation with high-pressure small-angle neutron scattering (SANS), an experimental technique uniquely capable of characterizing methane behavior in situ within shale nanopores at elevated pressures. Samples were created using Marcellus shale, a gas-generative formation comprising the largest natural gas field in the United States. Our results demonstrate that, contrary to the conventional wisdom that elevated drawdown pressure increases methane recovery, a higher peak pressure led to the trapping of dense, liquid-like methane in sub-2 nm radius nanopores, which comprise more than 90% of the measured nanopore volume, due to irreversible deformation of the kerogen matrix. These findings have critical implications for pressure management strategies to maximize hydrocarbon recovery, as well as broad implications for fluid behavior under confinement.

Water-in-CO2 Microemulsions Stabilized by an Efficient Catanionic Surfactant.

To facilitate potential applications of water-in-supercritical CO2 microemulsions (W/CO2 μEs) efficient and environmentally responsible surfactants are required with low levels of fluorination. As well as being able to stabilize water-CO2 interfaces, these surfactants must also be economical, prevent bioaccumulation and strong adhesion, deactivation of enzymes, and be tolerant to high salt environments. Recently, an ion paired catanionic surfactant with environmentally acceptable fluorinated C6 tails was found to be very effective at stabilizing W/CO2 μEs with high water-to-surfactant molar ratios (W0) up to ∼50 (Sagisaka, M.; et al. Langmuir 2019, 35, 3445-3454). As the cationic and anionic constituent surfactants alone did not stabilize W/CO2 μEs, this was the first demonstration of surfactant synergistic effects in W/CO2 microemulsions. The aim of this new study is to understand the origin of these intriguing effects by detailed investigations of nanostructure in W/CO2 microemulsions using high-pressure small-angle neutron scattering (HP-SANS). These HP-SANS experiments have been used to determine the headgroup interfacial area and volume, aggregation number, and effective packing parameter (EPP). These SANS data suggest the effectiveness of this surfactant originates from increased EPP and decreased hydrophilic/CO2-philic balance, related to a reduced effective headgroup ionicity. This surfactant bears separate C6F13 tails and oppositely charged headgroups, and was found to have a EPP value similar to that of a double C4F9-tail anionic surfactant (4FG(EO)2), which was previously reported to be one of most efficient stabilizers for W/CO2 μEs (maximum W0 = 60-80). Catanionic surfactants based on this new design will be key for generating superefficient W/CO2 μEs with high stability and water solubilization.

Pressure-Effects and Adaptation Mechanisms of Ambient and Deep-Sea Bacterial Enzymes

Submersible expeditions into the deepest parts of Earth's oceans have led to discoveries of organisms thriving in the extremes, raising questions on the limits of life and the functioning of their central biological macromolecules. Questions arise as to how life would be able to survive under such “harsh” conditions, and what adaptations may be present in these organisms’ proteins. Our major focus is on understanding biophysical effects of extreme pressure, which is a relatively underexplored condition for protein solutions. Investigating the effects of high hydrostatic pressure (HHP) on the biophysical properties of proteins, in conjunction with structural adaptations utilized by known piezophilic organisms to maintain proper function, provide better insight into how organisms are affected by and survive at such depths. The results gathered from these data can impact our use of pressure for sterilization of food products, our understanding of piezophilic adaptations, and enhance our understanding of the origins of life. Graphics processing unit (GPU)-accelerated OpenMM molecular dynamics simulations were used to explore pressure-effects on and pressure-adaptations within a central metabolic enzyme, dihydrofolate reductase (DHFR). In-silico comparisons of hydrogen bonding, collective motion, among other phenomena, were made between bacterial DHFRs of the mesophile (ambient pressure) Escherichia coli, the deep-sea piezophiles Moritella profunda and Moritella yayanosii, as well as mutants containing specific residues identified to be important in pressure-sensitivity. Furthermore, high-pressure small-angle neutron and X-ray scattering, fluorescence and other high-pressure experimental techniques conducted up to 3.5 kbar further probed the biophysical effects of HHP on E. coli and M. profunda DHFRs. The combined results from in-silico and in-situ techniques provide enhanced insight into the interplay between the sequence, structure, and hydration of proteins underpinning life inhabiting extreme pressures.

Anisotropic reversed micelles with fluorocarbon-hydrocarbon hybrid surfactants in supercritical CO2.

Previous work (M. Sagisaka, et al. Langmuir 31 (2015) 7479-7487), showed the most effective fluorocarbon (FC) and hydrocarbon (HC) chain lengths in the hybrid surfactants FCm-HCn (sodium 1-oxo-1-[4-(perfluoroalkyl)phenyl]alkane-2-sulfonates, where m = FC length and n = HC length) were m and n = 6 and 4 for water solubilization, whereas m 6 and n 6, or m 6 and n 5, were optimal chain lengths for reversed micelle elongation in supercritical CO2. To clarify why this difference of only a few methylene chain units is so effective at tuning the solubilizing power and reversed micelle morphology, nanostructures of water-in-CO2 (W/CO2) microemulsions were investigated by high-pressure small-angle neutron scattering (SANS) measurements at different water-to-surfactant molar ratios (W0) and surfactant concentrations. By modelling SANS profiles with cylindrical and ellipsoidal form factors, the FC6-HCn/W/CO2 microemulsions were found to increase in size with increasing W0 and surfactant concentration. Ellipsoidal cross-sectional radii of the FC6-HC4/W/CO2 microemulsion droplets increased linearly with W0, and finally reached ∼39 Å and ∼78 Å at W0 = 85 (close to the upper limit of solubilizing power). These systems appear to be the largest W/CO2 microemulsion droplets ever reported. The aqueous domains of FC6-HC6 rod-like reversed micelles increased in size by 3.5 times on increasing surfactant concentration from 35 mM to 50 mM: at 35 mM, FC6-HC5 formed rod-like reversed micelles 5.3 times larger than FC6-HC6. Interestingly, these results suggest that hybrid HC-chains partition into the microemulsion aqueous cores with the sulfonate headgroups, or at the W/CO2 interfaces, and so play important roles for tuning the W/CO2 interfacial curvature. The super-efficient W/CO2-type solubilizer FC6-HC4, and the rod-like reversed micelle forming surfactant FC6-HC5, represent the most successful cases of low fluorine content additives. These surfactants facilitate VOC-free, effective and energy-saving CO2 solvent systems for applications such as extraction, dyeing, dry cleaning, metal-plating, enhanced oil recovery and organic/inorganic or nanomaterial synthesis.

Tuning Micellar Structures in Supercritical CO2 Using Surfactant and Amphiphile Mixtures.

For equivalent micellar volume fraction (ϕ), systems containing anisotropic micelles are generally more viscous than those comprising spherical micelles. Many surfactants used in water-in-CO2 (w/c) microemulsions are fluorinated analogues of sodium bis(2-ethylhexyl) sulfosuccinate (AOT): here it is proposed that mixtures of CO2-philic surfactants with hydrotropes and cosurfactants may generate elongated micelles in w/c systems at high-pressures (e.g., 100-400 bar). A range of novel w/c microemulsions, stabilized by new custom-synthesized CO2-phillic, partially fluorinated surfactants, were formulated with hydrotropes and cosurfactant. The effects of water content (w = [water]/[surfactant]), surfactant structure, and hydrotrope tail length were all investigated. Dispersed water domains were probed using high pressure small-angle neutron scattering (HP-SANS), which provided evidence for elongated reversed micelles in supercritical CO2. These new micelles have significantly lower fluorination levels than previously reported (6-29 wt % cf. 14-52 wt %), and furthermore, they support higher water dispersion levels than other related systems (w = 15 cf. w = 5). The intrinsic viscosities of these w/c microemulsions were estimated based on micelle aspect ratio; from this value a relative viscosity value can be estimated through combination with the micellar volume fraction (ϕ). Combining these new results with those for all other reported systems, it has been possible to "map" predicted viscosity increases in CO2 arising from elongated reversed micelles, as a function of surfactant fluorination and micellar aspect ratio.

Effect of Fluorocarbon and Hydrocarbon Chain Lengths in Hybrid Surfactants for Supercritical CO2.

Hybrid surfactants containing both fluorocarbon (FC) and hydrocarbon (HC) chains have recently been shown to solubilize water and form elongated reversed micelles in supercritical CO2. To clarify the most effective FC and HC chain lengths, the aggregation behavior and interfacial properties of hybrid surfactants FCm-HCn (FC length m/HC length n = 4/2, 4/4, 6/2, 6/4, 6/5, 6/6, and 6/8) were examined in W/CO2 mixtures as functions of pressure, temperature, and water-to-surfactant molar ratio (W0). The solubilizing power of hybrid surfactants for W/CO2 microemulsions was strongly affected by not only the FC length but also by that of the HC. Although the surfactants having short FC and/or HC tails (namely, m/n = 4/2, 4/4, and 6/2) did not dissolve in supercritical CO2 (even at ∼17 mM, ≤400 bar, temperature ≤ 75 °C, and W0 = 0-40), the other hybrid surfactants were able to yield transparent single-phase W/CO2 mixtures identified as microemulsions. The solubilizing power of FC6-HCm surfactants reached a maximum (W0 ∼ 80 at 45 °C and 350 bar) with a hydrocarbon length, m, of 4. The W0 value of 80 is the highest for a HC-FC hybrid surfactant, matching the highest value reported for a FC surfactant which contained more FC groups. High-pressure small-angle neutron scattering measurements from FCm-HCn/D2O/CO2 microemulsions were consistent with growth of the microemulsion droplets with increasing W0. In addition, not only spherical reversed micelles but also nonspherical assemblies (rodlike or ellipsoidal) were found for the systems with FC6-HCn (n = 4-6). At fixed surfactant concentration and W0 (17 mM and W0 = 20), the longest reversed micelles were obtained for FC6-HC6 where a mean aspect ratio of 6.3 was calculated for the aqueous cores.

Shape Transitions in Supercritical CO2 Microemulsions Induced by Hydrotropes

The ability to induce morphological transitions in water-in-oil (w/o) and water-in-CO2 (w/c) microemulsions stabilized by a trichain anionic surfactant 1,4-bis(neopentyloxy)-3-(neopentyloxycarbonyl)-1,4-dioxobutane-2-sulfonate (TC14) with simple hydrotrope additives has been investigated. High-pressure small-angle neutron scattering (SANS) has revealed the addition of a small mole fraction of hydrotrope can yield a significant elongation in the microemulsion water droplets. For w/o systems, the degree of droplet growth was shown to be dependent on the water content, the hydrotrope mole fraction, and chemical structure, whereas for w/c microemulsions a similar, but less significant, effect was seen. The expected CO2 viscosity increase from such systems has been calculated and compared to related literature using fluorocarbon chain surfactants. This represents the first report of hydrotrope-induced morphology changes in w/c microemulsions and is a significant step forward toward the formation of hydrocarbon worm-like micellar assemblies in this industrially relevant solvent.

Nanostructures in Water-in-CO2 Microemulsions Stabilized by Double-Chain Fluorocarbon Solubilizers

High-pressure small-angle neutron scattering (HP-SANS) studies were conducted to investigate nanostructures and interfacial properties of water-in-supercritical CO2 (W/CO2) microemulsions with double-fluorocarbon-tail anionic surfactants, having different fluorocarbon chain lengths and linking groups (glutarate or succinate). At constant pressure and temperature, the microemulsion aqueous cores were found to swell with an increase in water-to-surfactant ratio, W0, until their solubilizing capacities were reached. Surfactants with fluorocarbon chain lengths of n = 4, 6, and 8 formed spherical reversed micelles in supercritical CO2 even at W0 over the solubilizing powers as determined by phase behavior studies, suggesting formation of Winsor-IV W/CO2 microemulsions and then Winsor-II W/CO2 microemulsions. On the other hand, a short C2 chain fluorocarbon surfactant analogue displayed a transition from Winsor-IV microemulsions to lamellar liquid crystals at W0 = 25. Critical packing parameters and aggregation numbers were calculated by using area per headgroup, shell thickness, the core/shell radii determined from SANS data analysis: these parameters were used to help understand differences in aggregation behavior and solubilizing power in CO2. Increasing the microemulsion water loading led the critical packing parameter to decrease to ~1.3 and the aggregation number to increase to >90. Although these parameters were comparable between glutarate and succinate surfactants with the same fluorocarbon chain, decreasing the fluorocarbon chain length n reduced the critical packing parameter. At the same time, reducing chain length to 2 reduced negative interfacial curvature, favoring planar structures, as demonstrated by generation of lamellar liquid crystal phases.

Low Fluorine Content CO2-philic Surfactants

The article addresses an important, and still unresolved question in the field of CO(2) science and technology: what is the minimum fluorine content necessary to obtain a CO(2)-philic surfactant? A previous publication (Langmuir 2002, 18, 3014) suggested there should be an ideal fluorination level: for optimization of possible process applications in CO(2), it is important to establish just how little F is needed to render a surfactant CO(2)-philic. Here, optimum chemical structures for water-in-CO(2) (w/c) microemulsion stabilization are identified through a systematic study of CO(2)-philic surfactant design based on dichain sulfosuccinates. High pressure small-angle neutron scattering (HP-SANS) measurements of reversed micelle formation in CO(2) show a clear relationship between F content and CO(2) compatibility of any given surfactant. Interestingly, high F content surfactants, having lower limiting aqueous surface tensions, γ(cmc), also have better performance in CO(2), as indicated by lower cloud point pressures, P(trans). The results have important implications for the rational design of CO(2)-philic surfactants helping to identify the most economic and efficient compounds for emerging CO(2) based fluid technologies.

Soft fluctuating surfactant membranes in supercritical CO2-microemulsions

The bending rigidity of surfactant membranes in novel bicontinuous CO(2)-microemulsions of the type H(2)O/NaCl-scCO(2)-Zonyl FSH/Zonyl FSN 100 was determined using both high pressure small angle neutron scattering and neutron-spin echo spectroscopy. As an important result it was found, that the stiffness of the membrane increases solely by an increase of the pressure.

Hydrocarbon Metallosurfactants for CO2

Cobalt and nickel salts of the highly branched trichain anionic surfactant sodium 1,4-bis(neopentyloxy)-3-(neopentyloxycarbonyl)-1,4-dioxobutane-2-sulfonate (TC14) are shown to be soluble in dense CO(2) at concentrations up to 6 wt % at 500 bar pressure. This is a remarkably high solubility for such hydrocarbon transition metal surfactants in CO(2). High-pressure small-angle neutron scattering (HP-SANS) has been used to study the surfactant aggregates in a normal organic solvent, cyclohexane, dense CO(2), and also mixtures of these two pure solvents. The results show that transition metal TC14 derivatives are viable compounds for incorporating reactive and functional metal ions into CO(2).

Surfactant Aggregation in CO2/Heptane Solvent Mixtures

The effect of improving "solvent quality" of pure liquid CO(2) with a heptane cosolvent on the phase behavior and micellization of commercially available surfactants has been explored using high-pressure small-angle neutron scattering (HP-SANS). The nonionic C(12)E(5) was found to be highly soluble in both pure CO(2) and the solvent blends, but no aggregation was detected by HP-SANS for any of the compositions studied, even up to 12 vol % surfactant. On the other hand, improving CO(2) solvent quality by adding heptane above 30 vol % promoted solubility and aggregate formation with normal sodium bis(ethylhexyl)sulfosuccinate (AOT). The solvent quality index Hildebrand solubility parameter, used to predict surfactant aggregation in pure hydrocarbon solvents (Langmuir, 2008, 24 (21), 12235-12240) has been tested here for CO(2)-heptane mixtures. The results show how solubility and efficiency of AOT, a commercially viable, well-known, and commonly used surfactant, can be boosted in alkane-containing CO(2)-rich fluids compared to pure CO(2) alone.

High-pressure small-angle neutron scattering studies of glucose isomerase conformation in solution

Small-angle neutron scattering (SANS) of solutions of glucose/xylose isomerase fromStreptomyces rubiginosuswas measured as a function of pressure. It is shown that the structure of the enzyme in solution as seen by SANS is practically the same as that in the crystal and does not change with pressure up to 150 MPa. This reflects the unusually high structural stability of this material, which makes it extremely interesting to use as a secondary standard for pressure-dependent SANS experiments. This lack of pressure dependence of the SANS data also indicates that any possible change in hydration of the protein induced by pressure is not visible in the SANS curves. An appropriate correction procedure must be used for the SANS data in order to account for the distortion of the intensity curve due to hard-sphere and electrostatic interactions. After this correction, the isomerase can be readily used as a secondary standard for SANS measurements.

Designed CO2‐Philes Stabilize Water‐in‐Carbon Dioxide Microemulsions

Wrapping up water: Two non-fluorinated CO2-philic surfactants are used to generate water in carbon dioxide microemulsion dispersions. Detailed analyses of high-pressure small-angle neutron scattering data provide evidence for formation of spherical D2O nanodroplets (red), stabilized by surfactant interfacial monolayers (lines), and dispersed in CO2 (yellow in the schematic scattering length density (sld) profile). Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2002/2006/z600397_s.pdf or from the author. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

High pressure small-angle neutron scattering study of the aggregation state of β-lactoglobulin in water and in water/ethylene-glycol solutions

High-pressure SANS experiments have been performed on acidic dilute solutions of the dimeric protein β-lactoglobulin. To evidence the solvent effect on the protein stability during compression, two different solvents, D 2O and a 50% w/w mixture of water and ethylene-glycol have been considered. Data confirm that pressure induces dissociation in both solvents, even if β-lactoglobulin shows an higher stability in 50% ethylene-glycol. An original global fitting procedure has been used to derive the thermodynamic parameters that describe the dissociation equilibrium. As a result, the role of the solvent in protein dissociation has been observed to reflect on volume and compressibility changes.

Self-Assembly at High Pressures: SANS Study of the Effect of Pressure on Microstructure of C8E5 Micelles in Water

We present the results of a high-pressure small-angle neutron scattering study of the effect of pressure on surfactant microstructure. The study was carried out on a solution of 1 wt % C8E5 in D2O at 29.4 °C and pressures up to 310 MPa. The C8E5 micelles that form under these conditions are noninteracting. We find that applying pressure leads to a pronounced decrease in the micelle radius of gyration and the forward scattering intensity over the pressure range from ambient to 150 MPa. The partial molecular volume of the surfactant and the extent of hydration of the surfactant head groups in the micelle were also determined using the method of solvent contrast variation. Both quantities decrease with the application of pressure up to 150 MPa. Core−shell model fits to the scattering spectra over the entire q-range indicate that the shell radius decreases, while the hydrophobic core radius increases slightly with pressure. The pressure dependence of the shell radius is notably similar to that observed for the radius of gyration. Collectively, these observations lead to the conclusion that the effect of pressure on C8E5 micellization is to induce the dehydration of surfactant head groups and the collapse of the hydrophilic micelle shell at pressures between ambient and 150 MPa.

Micellization of economically viable surfactants in CO 2

Stability and aggregation structures of various economically viable surfactants for CO 2 are reported. The compounds are either commercially available octylphenol nonionics (Triton X-100, X-100 reduced, and X-45) or custom-made analogues of aerosol-OT (J. Am. Chem. Soc. 123 (2001) 988). These were selected to reveal the influence of chain terminal group structure, namely highly methylated t-butyl units, on solubility and aggregation in CO 2. In addition the mean ethylene oxide block length is varied for the Triton surfactants (X-100 ∼ EO 10, X-45 ∼ EO 8). High-pressure small-angle neutron scattering (SANS) experiments revealed the presence of aggregates, consistent with spheroidal reverse micelles. The nonionics show a temperature and pressure dependence on solubility. These results confirm the special affinity of highly methyl-branched tails for CO 2. However, none of these systems were able to disperse significant amounts of water or brine; therefore hydrated reversed micelles or microemulsion droplets were not stabilized. Hence the utility of these cheap methyl-branched surfactants in CO 2 is limited, and so groups of greater CO 2-philicity are needed to achieve the goal of water–hydrocarbon surfactant–CO 2 dispersions.